Fluorinated ethylenically unsaturated organic sulfide compounds and polymers



United States Patent This invention relates to novel fiuorinated organicsulfides, to their ,preparation, and to polymers obtained from them.More particularly, this invention relates to novel fiuorinated.ethylenically unsaturated :organic sulfides, to theirprepa'ration, andto polymers thereof.

The present application is a continuation-in-part of Harris Ser.-No.:855,279, now abandoned, which was filed Nov. 25, 1959 and wascopending at the timeof filing the instant application.

Organic sulfides are a Well-knoWnclass of compounds .which are alsocalled thioethers. The compounds arecharacterized by a divalent sulfuratom bonded to-two organic groups. Organic sulfides in which the organicgroups are substantially hydrocarbon have been studied extensively andattention has also been given to sulfides in which the organic groupsbear a limited number of substituents. However, there :is very :littleknown about highly iluori- 'nated organic :sulfides. In particular,organic sulfides which have, iastsubst'ituent groups on thesulfur, ahighly fluorinated 'alkyl group and Ja'polymeriza'ble vinyl group bondedto fiuorine or xfiuorinated ialkylth'io radicals, are unknown. Thepreparation and characterization of this previously run'known class .ofcompounds represents an advance in useful knowledge and it is with thisclass of compounds that the present inventionis concerned.

It is an object of this invention to iprovide new fluorinated organicsulfides. A .further' object of this invention is to provide fiuorinatedunsaturated organicLsulfides containing a novel combination of a highlyfiuorinated alkyl group and a polymerizable vinyl group and methods fortheir preparation. A further object -is to provide novel ,lpolymers ofthese -new fiuorinated-organic sulfides. Still .anotherobjectistoprovidenovel polymers of fluorinated .organic sulfides whichare usefulas treating agents for porous materials to :impart water-repellentproperties there- -to. Otherobjectswillrappear hereinafter. inventionwhich provides a new class of polyfiuorinated These and-otherobjectsareaccomplished by the present organic'sulfides'whichareethylenic compounds having a monovalent polyfluoroallcylthio groupbonded to one of the-ethyleniccarbons and-bonded to the same carboneither .hydrogen,-a halogen of atomic 'number of at least 9 and not morethan .35 (i.e., fluorine, chlorine, or bromine) or a,polyfluoroalkylthio group; the other ethylenic carbon has onevalence'satisfied by-fluorine or a polyfluoroalkylthio :group .and theremaining valence satisfied by hydrogen, a halogen of atomic number ofat least 9 and not more than 35, a polyfiuoroalkylthio group, ahydrocarbylthio group, a hydrocarbyloxy/group, or a -di(hydrocarbyl)amino group. Each of the aforesaid monovalentpolyfluoroalkylthio groupscontains divalent sulfur bonded through one valen'ce to Y apolyfiuorozillz-y'l group consisting *ofcarbon and fluorine and atmostone hydrogen or chlo- "rine, which, if present, is on the omegacarbon.

The new organic'sulfides'o'f this invention have'the fol lowingstructural formula:

Patented June 20, .1967

wherein R is a polyfluorinated alkylgroup having bonded to the terminalcarbon atom at most one hydrogen orchlorine, i.e., w-hydro or chloro,the remaining elements in said polyfiuorinated alkyl group being carbonand fluorine; Y is hydrogen, a halogen of atomic number of at least 9and not more than 35 (i.e., fluorine, chlorine, or-brornine) or an RSgroup; W is fluorine or an RS group; and X is hydrogen, a halogen ofatomic number of at least 9 and not more than 35 (i.e., fluorine,chlorine, or bromine), an RS, or R'S, RO, or R N group, wherein R is ahydrocarbon radical. In this formula, each R is a perfluoro alkyl group,omega-hydroperfluoroalkyl group, or omegachloroperfiuoroalk-yl group,which polyfluorinated alkyl group in a preferred form of the inventionis of at most 8 carbons;'and each R moiety of X is ahydrocarbon groupwhich can be alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl oralkaryl, and which in a preferred form of the invention is of at most 12carbons. For expediency, R will usually not be more than '8. Inspecially preferred forms of the invention, Y and X are fluorine or IRS.

This invention -is generic 'tothe new fiuorinated organic sulfides,including fiuorovinyl organic sulfides, and to polymers obtainable from:these fluorovinyl organic sulfides. The polymers, i.e., thehomo-polymers and copol-ymers, obtained by polymerization of the newfluorovinyl organic sulfides form apart of this invention.

The new ,rpolyfiuorinated unsaturated organic sulfides can be obtainedby vprocesses which comprise deha'logenation or dehydrdhalogenation ofsaturated polyfluorinated organic sulfides which are halogenated ethanesbearing from one to 'four omega-hydroperfiuoroalkylthio,omegachloroperfiuoroalkylthio or :perfluoroalkylthi o substituents, atleast-one halogen, and at most two hydrogens'of which at mostone isbonded to eachethanocarbon. These new ,polyfiuorinated ethylenicsulfides can also be obtained. by reaction of a bis(polyfiuoroalkylthio) acetylene with a polyfiuoroalkanethiol, apolyfiuoroalkanesulfenyl halide, a hydrocarbylthiol,ahydrocarbylsulfenylJhalide, a hydrocarbyl alcohol, or adi(hydrocarb.yl.):amine. The processes of preparation and the generalstructure of the organic sulfides which are employed in each process aredescribed more fully hereinafter.

Examples of monomeric fluor'inated organic sulfides which fall withinthe scope of this invention are as follows:

1- 6H-perfluorohexylthio) -2- (trifiuoromethylthio -2- cyclobutoxy)ethylene,

1- 8-chloroperfluorooctylthio -2- (trifiuoromethylthio2-(2-butenyl-1-oxy) ethylene,

1,2-bis (trifluoromethylthio -2- propargyloxy) ethylene,

1,2-bis (trifluoromethylthio -2- (p-toloxy) ethylene,

1- (perfiuoroethylthio -2- (trifluoromethylthio) -2- (mphenylphenoxyethylene,

1,2-bis (trifluoromethylthio -2- (diethylamino ethylene,

1,2-bis (trifluoromethylthio -2- (N-methyl-N-octylarnino ethylene, and

1,2-bis (trifluorornethylthio) -2- (N methylanilino) ethylene.

Compounds, such as these, having polyfiuoroalkylthio substituentscontaining up to 12 carbon atoms are entirely practical, since suitablepolyfiuoroalkyl intermediates are presently available for theirpreparation.

The new monomeric compounds of this invention are generally thermallystable, non-corrosive materials which can be stored in conventionalcontainers of glass or metals. Normal precautions should be taken toprevent undue inhalation of the vapors of the compounds or to avoidunnecessary'or prolonged contact with the skin. The compounds have arelatively mild odor which is not obnoxious. The compounds are usuallycolorless liquids or low-melting solids which can be distilled withlittle or no decomposition. They are soluble in the conventional organicsolvents, e.g., acetone, alcohol, dimethylformamide, ether, benzene,octane, cyclohexane, and the like. The compounds are solvents forpolymeric materials, e.g., lowmelting poly(tetrafiuoroethylene)resin.

The new fiuorovinyl organic sulfides, of the formula indicated below,are polymerizable monomers. They can, when polymerized alone, formhomopolymers or, when polymerized with other polymerizable monomers,such as monomeric ethylenically unsaturated polymerizable compounds,form copolymers. To illustrate, the new compounds form'copolymers withstyrene, methyl methacrylate, acrylonitrile, diviny-lbenzene,hexafiuoropropene, butadiene, tetrafiuoroethylene,chlorotrifiuoroethylene, and the like. The polymers, includinghomopolymers and copolymers, have as a characteristic recurring unit thestructure in which R has the meaning given hereinbefore, X is hydrogen,fluorine, chlorine or bromine, and Y is fluorine, chlorine or bromine.

The polymers obtained from the fluorovinyl sulfides can have a widerange of molecular weights. The molecular weights may be relatively low,e.g., 1000 or lower, or they can be of intermediate range, e.g., 5000 to20,000, or the molecular weights may be as high as 50,000 or more. Thedegree of polymerization, i.e., the molecular weight, of the polymer isdetermined to some extent by the conditions of polymerization. Ingeneral, the polymers which are obtained have molecular weights of about1000 to 20,000.

Polymerization of the monomers is accomplished by conventional andwell-known methods, e.g., by photochemical action.

In physical characteristics, the polymers range form clear low-meltingtacky products to clear, tough and tackfree materials which soften atrelatively high temperatures. The polymers are soluble in many organicliquids, including dimethylformamide, tetrahydrofuran,tetrahydrothiophene-1,1-dioxide, and butyrolactone. The polymers areuseful in coating compositions for porous objects including fabrics,wood, brick and stone.

The following examples, in which parts are by weight, illustrate thedetails of preparing representative compounds of the invention. Theinitial reactants, i.e., the saturated halogenated sulfides, areobtained by conventional methods which are also illustrated forrepresentative sulfides in the examples.

EXAMPLE I A. 1,2,2-triflu0r0ethyl trifiuoromethyl sulfide A mixture of64 parts of trifluoromethanethiol and 51 parts of trifluoroethylene isloaded into a quartz reaction vessel, the length of which is six timesits diameter, and which is fitted with a condenser containing a solidcarbon dioxide-acetone mixture. While the mixture is refluxing, it isirradiated with a spiral-shaped low pressure, quartz mercury resonancelamp, which is fitted around the outside of the reactor. After a periodof irradiation of about 25 minutes, the resulting mixture is distilledthrough a large spinning band still. There is obtained 86 parts (75% oftheory) of product distilling at 46-51 C. (mostly 50-51 C.). Thefluorine nuclear magnetic resonance pattern of the lower boiling (46-50C.) portion of this material indicates that it is a mixture, the majorcomponent of which is 1,2,2-trifluoroethyl trifiuoromethyl sulfide. Theminor component is the isomeric 1,1,2-trifluoroethyl trifiuoromethylsulfide. The fluorine nuclear magnetic resonance pattern of the fractionboiling at 50-51 C. confirms that it is pure 1,2,2-trifluoroethyltrifluoromethyl sulfide.

Analysis.-Calcd for C H F S: F, 61.9; S, 17.4. Found: F, 62.1; S, 17.3.

Chlorine (dried by passage through concentrated sulfuric acid) is passedthrough 1,2,2-trifluoroethyl trifiuoromethyl sulfide which is beingrefluxed and irradiated with an ultraviolet lamp. Distillation of thereaction mixture yields l-chloro-1,2,2-trifiuoroethyl trifiuoromethylsulfide (C HClF S; B.P. 62 C.; N 1.3380) and 1,2-dichloro 1,2,2trifluoroethyl trifiuoromethyl sulfide (C Cl F S; B.P. 84 C.; n 1.3560).

An'alysis.-Calcd for C HClF S: S, 14.7; C1, 16.2. Found: S, 14.7; C1,16.0.

Analysis.- Calcd for C Cl F S: CI, 28.0; F, 45.0; S, 12.7. Found: Cl,27.7; F, 45.2; S, 12.5.

C. T rifluorovinyl trifiuoromethyl sulfide A glass reaction vessel isemployed which is equipped with an addition funnel and a short pathstill head joined to a trap cooled with a solid carbon dioxide-acetonemixture. The vessel is charged with 25 parts of potassium hydroxide andit is then heated to 135 C. The addition funnel is adjusted to bring itstip below the surface of the melted potassium hydroxide and 10 parts ofl-chloro- 1,2,2-trifluoroethyl trifiuoromethyl sulfide is added over aperiod of 20 minutes to the potassium hydroxide which is maintained at130 C. The reaction products pass through the still head and arecollected in the trap. There is obtained 5.48 parts of liquid productswhich are distilled through an efiicient fractionating column to yield asmall amount of trifiuoromethyl trifiuorovinyl sulfide, boiling at 1820C. The compound, whose structure is confirmed by the nuclear magneticresonance spectrum, has the formula CF -SCF=CF EXAMPLE 11 Using areaction vessel and procedure described in Example I, 33.5 parts of1,2,2-trifiuoroethyl trifiuoromethyl sulfide (prepared as in Example IA)is added over a period of 0.5 hour to 50 parts of potassium hydroxide at130-135" C. Thereis collected in the trap 27.35 parts of reactionproducts which are distilled through an efiicient fractionating column.There is obtained 6.82 parts of trifiuoromethyl 1,2-difluorovinylsulfide, boiling at 37- 38 C.; 11 1.3271. The identity of the compound,which has the structure CF -SCF=CFH, is confirmed by the nuclearmagnetic resonance spectrum and by elemental analysis.

Analysis.Calcd for C HF S: C, 22.0; H, 0.6; F, 57.9; .S, 19.5. Found: C,23.0; H, 1.1; F, 57.9; S, 19.5.

In the fractional distillation of the crude liquid reaction products,there is obtained 3.32 parts of foreshots, boiling at 22-37 '0, 1.3249,"which are shown by gas chromatography to contain about 85% oftrifluoromethyl 1,2-difluorovinyl sulfide. About '12 parts of thestarting reactant, boiling up to 57 C., arerecovered.

A mixture of parts of trifiu'oromethanethiol and 40 parts ofchlorotrifiuoroethylene is irradia'ted'as described in Example I-A. Upondistillation of the reaction mixture through a large spinning bandstill, there is obtained 26.6 parts (62% of theory) of2-chloro-1,1,2-trifluoroethyl trifiuoromethyl sulfide-distilling at66-67 C., 12 1.3339- 1.3341.

Analysis.-Ca'lod for 'CI-IClFgS: C, 16.5; H, 0.5; F, 52.1. Found: C,16.7; H, 0.6; F, 52.3.

Using a reaction vessel and procedure described in Example I-C, 15 partsof '2-'chloro-1,1,2=trifiuoroethyl trifiuorome'thyl sulfide are reactedwith 25 parts of potassium hydroxide at 130135 C.

The reaction is repeated using 3 8.4 parts of the sulfide and 25 partsof potassium hydroxide.

The reaction products 'are combined and distilled to yield 9.2 parts ofa water-white fraction boiling at 40- 57 C.; 5, 1.3493. This fractionis'carefully distilled through an e'fiicient fractionating column toyield 2- chloro-1,2-difluorovinyl trifiuoromethyl sulfide, boiling at58-61 C.; 115 1.3588. A sample of this fraction, purificd by gaschromatography, distills sharply at 57 -C. The identity of the compound,which has the formula CF -SCF=CFCl, is confirmed by the nuclear magneticresonance spectrum. The compound is also 'ch'aracteri'zed by anunsaturation band at 6105 microns in the infrared.

An'alysis.Calc"d for C F ClS: F, 47.8; C1, 17.9. Found: F, 48.4; Cl,170.

A mixture of 18 parts of 1,1,2,Z-tetrafluoroethanethidl prepared by theX-ray initiated addition of hydrogen sulfide to tetrafiuoroethylene and15 pars of trifluoroethylene is irradiated for a period of 18 hours asdescribed in Example I-A. Upon distillation of the reaction mixturethrough a small spinning band still, there is obtained 20.3 parts of1,2,2-trifiuoroethYl 1,'1,'2,2-tetrafluoroethyl sulfide distilling at1=O4-l0'5 C.,n ,'-1.3383.

A-nalysis.Calcd for C H F S: 1 ,6 15; S, 14. 8. Found: F, 61.2; S, 15.4.

A mixture of l0 parts of 1,2,2-trifluoroethyl 1,1,2,2- tetrafiuoroethylsulfide and 6 parts of potassiumhydroxide, contained in a vessel fittedwith a short path distillation head connected to a solid carbondioxide-acetone cooled trap, is 'heated to 125-130 C. for a period of 2hours. The trap contents (7.33 parts, 81% of theory) are dried over amixture'of anhydrous magnesiumsulfate and calcium chloride and thendistilled through -a spinning band still. There is obtained 5.60 partsof l,2-'difluorovinyl 1,l,2,2-tet-rafluoroethyl sulfide as a Water-whiteliquid distilling at 86-88 C.; 11 13528-13541. The nuclear magneticresonance spectrum confirms the assigned structure. The compound is alsocharacterized by an unsaturation band at 6.1 microns in the infrared.

6 An'alysi's-Calcd for C H F S: F, 58.1;8, 16.3. Found: F, 58.0; S,16.2.

EXAMPLE V '1,2-b1's(trifluoromethylthio) ethylene A solution of 10.1parts of potassium hydroxide in 47 parts of anhydrous ethanol is addedduring .20 minutes to a solution, cooled to 5 C., of 47.5 parts ofl-bromo- 1,2 bis(trifluoromethylthio)ethane in 39.5 parts of absoluteethanol. The reaction mixture is kept below 30 C., and after beingstirred for 30 minutes it is poured into a large excess of ice water.The organic layer is washed with water, dried over magnesium sulfate anddistilled. There is obtained 13.5 parts (38%) of l;2=bis(trifluoromethylthio)ethylcne as a colorless liquid distilling at92- 98 C. The presence of two isomers in a r-atio of 3:1 is shown 'by agas chromatogram of the product. The isomers, purified by gaschromatography, are characterized and identified as follows: cis-isomerB.P. 97 C., n 1.3832, infrared absorption at 3.25 microns (CH),6.4 microns '(SC=C), 13.2 microns -(SCF and -14-micron region (I-IC CH);trans isomer-ZBLP. 96.5 C., n5 1.3886, infrared absorption at 3.25microns (OH), 10.8 microns (HC CH), and 13.2 microns (SCF'Analysis.-Calcd for C H F S F, 50.0; S, 28.1. Cis, found: F, 49.3; S,28.0. Trans, found: F, 49.3; S, 28.0.

Examples I-V illustrate the preparation of typical compounds of theinvention employing a dehydrohalogenation process. Organic sulfides ofthe type described earlier which have hydrogen bonded to a'car bon ofthe ethano group 'are usually operable in the process. For example, byusing the process of Examples I-V, omega-hydroperfluoropropyltrifiuorovinylsulfide is obtained from omegahydroperfiuoropropyl1-chloro-1,2,2-trifluoroethyl sulfide, omega-chloroperfiuorooctyl1,2-difiuorovinyl sulfide is obtained fromomega-chloroperfiuorooctyl-1,2,2-trifiuoroethyl sulfide,chlorodifiuoromethyl 2 bromo-l,2 -diflu0rovinyl sulfide is obtained fromc'hlorodifiuoromethyl 2- bromo-1,1,2-trifiuoroethyl sulfide,1,1.,2,2-tetrafiuoroet-hyl 1,2-difluorovinyl sulfide is obtained from1,1,2,2-tetrafluoroethyl 1,2,2-trifiuoroethyl sulfide andl-(perfluoromethylthio)-2-porfiuoroethylthio)ethylene is obtained froml-chlorol (.perfiuoromethylthio )--.2- (.perfluoroethylthio)ethane.

EXAMPLE VI A glass reaction vessel is employed which is equipped with athermometer, an addition funnel and a reflux condenser through whichwater at a temperature of 35-40 C. is circulating. The condenser isconnectedto a trap cooled with a solid carbon dioxide-acetone mixtureand fitted with a tube charged with calcium chloride. The reactionvessel is charged with 22 parts of methanol, 5.8 parts of zinc dust and0.02 part of granular zinc chloride. The reaction mixture is heated torefluxing temperature and a solution of 20.8 parts1,2-dichlorotrifiuoroethyl trifluoromethyl sulfide in 10 parts ofmethanol is added dropwise. After addition is completed, the mixture isrefluxed for 1.5 hours. i

The reaction is repeated as described above except 20.4 parts of1,2-dichlorotrifiuoroethyl trifluoromethy-l sulfide is employed.

The reaction products from both runs which are collected in the trapsare combined and they are distilled through an efiicient fractiouatingcolumn equipped with a condenser through which methanol cooled withsolid carbon dioxide is circulating. There is obtained 14.2 parts oftrifluorome'thyl trifiuorovinyl sulfide, :boiling at 18.0- 18.5 C. Thecompound is characterized by an unsaturation band at 5.71 microns in theinfrared.

Analysis-Calcd for C F S: S, 17.6. Found: S, 182.

Example VI illustrates the method 'of preparing the new compounds by adeh'a'logenation process. This method of preparation is particularlyuseful when the initial reactant is an organic sulfide as definedearlier in which the ethano group bears on each carbon a halogen ofatomic numher 17-35, inclusive. Examples of other polyfiuorinatedunsaturated organic sulfides which may be prepared by the process ofExample VI are perfluorobutyl trifluorovinyl sulfide from perfiuorobutyl 1,2-dichloro-1,2,2-trifiuoroethyl sulfide, difiuoromethyltrifluorovinyl sulfide from difiuoromethyl1,2-dibromo-1,2,2-trifluoroethy1 sulfide, omega-hydroperfluorohexyltrifiuorovinyl sulfide from omega-hydroperfluorohexyl1,2-dichloro-1,2,2-trifiuoroethyl sulfide and1,2-bis(3-chloroperfiu'oropropylthio)ethylene from1,2-dichloro-1,2-bis(3-chloroperfluoropropylthio)ethane. 1

EXAMPLE VII Tris( trifluoromethylthio ethylene A mixture of 19.6 partsof bis(trifiuoromethylthio)- acetylene and 32 parts oftrifluoromethanethiol is irradiated for a period of 3 days as describedin Example I-A. Upon distillation of the reaction mixture there isobtained 11.1 parts (39%) of tris(trifluoromethylthio)ethylenedistilling at 42-47.5 C. under a pressure of 31 mm. of mercury;1.4004-1.4013. The compound is characterized by an unsaturation band at6.5 microns in the infrared.

Analysis.-Calcd for C HF S F, 52.0; S, 29.3. Found: F, 51.1; S, 29.8.

EXAMPLE VIII Tris(trifluoromethylthylthio) chloroethylen e A mixture of14.8 parts of bis(trifluoromethylthio)- acetylene and 11 parts oftrifiuoromethanesulfenyl chloride is irradiated for a period of 18 hoursas described in Example I-A. Upon distillation of the reaction mixturethere is obtained 11.3 parts (47.4%) oftris(fluoromethylthi)chloroethylene distilling at 52-60 C. under apressure of 25 mm. of mercury; 11 14298-14308. The compound ischaracterized by an unsaturation band at 6.75 microns in the infrared.

Analysis.Calcd for C ClF S Cl, 9.8; F, 47.2. Found: CI, 10.3; F, 46.5.

EXAMPLE IX 1,2-bis(trifluoro methylthio)-2-(methoxy)ethylene A solutionof 5 parts of bis(trifluoromethylthio)acetylene in 4 parts of methanolis added dropwise to a solution of 0.25 part of sodium methoxide in 20parts of anhydrous methanol. After the initial exothermic reaction isover the mixture is heated at 100 C. for 15 minutes, and is then pouredinto a large excess of water. The organic layer is removed by twoextractions with 18 parts of ether. The extracts are dried overanhydrous magnesium sulfate and then distilled to obtain 3.61 parts(63%) of 1,2 bis(trifiuoromethylthio) 2 (methoxy)ethylene which distillsat 134-136 C., n 1.4010.

Analysis.Calcd for C H F OS C, 23.3; H, 1.6;

I s, 24.4. Found: c, 23.3; H, 2.2; s, 24.3.

EXAMPLE X 1,2-bis( trifluoromethylthio -2- morpholino) ethylene Asolution of 1.25 parts of morpholine in 7.1 parts of anhydrou ether isadded to a stirred and cooled solution of 3.2 parts ofbis(trifluoromethylthio)acetylene in 7.1 parts of anhydrous ether. Thereaction mixture is filtered to remove a small amount of white solid,and ether is distilled from the filtrate at atmospheric pressure. Theresidue is distilled under reduced pressure to yield 3.07 parts (69%) ofcrude 1,2-bis(trifluoromethylthio)-2- (morpholino)ethylene boiling overa range of temperature up to 56 C. at 0.18 mm., n 14589-14618.Redistillation of this product yields a purified fraction, B.P. 42-54C./0.24 mm. and n 1.4578.

Analysis.Calcd for C H F NOS F, 36.4; S, 20.5. Found: F, 36.2; S, 19.8.

Examples VII-X illustrate the method of preparing typical compounds ofthe invention by addition reactions ofbis(polyfiuoroalkylthio)acetylenes. This method is particularly usefulfor preparing polyfiuorinated ethylenic organic sulfides having twovicinal polyfluoroalkylthio groups and other substituents on theethylenic carbons. For example, by using the process of Examples VII-X,1 methylthio 1,2 bis(12 H perfiuorododecy1thio)- ethylene is obtainedfrom methanethiol and bis(l2-H-perfiuorododecylthio)acetylene, 1 bromo 2phenylthio- 1,2 -bis(trifiuoromethylthio)ethylene is obtained frombenzenesulfenyl bromide and bis(trifluoromethylthio) acetylene, 1benzyloxy 1,2 bis(trifiuoromethylthio) ethylene is obtained from benzylalcohol and bis(triflu0romethylthio)acetylene, andl-piperidino-1,2-bis(trifluoromethylthio)ethylene is obtained frompiperidine and bis- (trifluoromethylthio) acetylene.

EXAMPLE XI A small quartz tube which is equipped with a condensercontaining a mixture of solid carbon dioxide and acetone is charged with5 parts of triflu-oromethyl trifiuorovinyl sulfide. The charged tube isirradiated for 2.5 days with a spiral-shaped low pressure mercuryresonance lamp which is fitted around the quartz tube. Refluxing of thesulfide which occurs initially diminishes as polymerization proceeds andthere is substantially no refluxing at the end of the period ofirradiation. The reaction product is freed of volatile materials underreduced pressure and there is recovered 1.32 parts of the originalunsaturated sulfide reactant mixed with a small amount of the dimer ofthe sulfide. There remains about 3.5 parts of viscous tacky productwhich is a polymer of trifluoromethyl trifiuorovinyl sulfide.

Analysis.Calcd. for (C F S) S, 17.6. Found: vS, 18.5.

The process described in Example XI can be used to prepare homopolymersand copolymers broadly of polyfiuo-roalkyl polyfluorovinyl sulfides.Thus, omega-chloroperfluorooctyl, 1,2-difluorovinyl sulfide andtrifiuoromethyl 1,2-difluorovinyl sulfide are polymerized to soft clearpolymers. Perfiuorobutyl trifiuorovinyl sulfide is copolymerized withstyrene to yield clear. products whose composition may contain from10-90 mole percent of the fluorovinyl sulfide. Difluoromethyltrifluorovinyl sulfide and methyl methacrylate are copolymerized toyield clear products having from 10-90 mole percent of the fluorovinylsulfide. The ratio of components in the copolymers is determined to alarge extent by the proportions in which the monomers are mixed prior toirradiation.

EXAMPLE XII Tetrakis triflworome thylthio) ethylene A mixture of 10parts of carbon tetrabromide and 40 parts ofbis(trifluoromethylthi0)mercury is placed in a glass reactor fitted witha dropping funnel, stirrer, and access to the atmosphere through a trapcooled in a mixture of solid carbon dioxide and acetone. The reactor isplaced in an oil bath, and the bath is heated slowly. When thetemperature reaches C. a strongly exothermic reaction takes place, andafter the reaction subsides the bath temperature is raised to C. andkept there for 3 hours. Finally, the system is evacuated with a Waterpump, causing the product to distill from the reaction vessel into thecooled trap. The contents of the trap are distilled in a fractionatingcolumn, and 3.0 parts of impure product boiling at 62-83 C. at 74 mm. isobtained. Fractionation of this product by preparative-scale gaschromatography yields a pure traction, B.P. 59 C./ 10 mm., n 1.4205,which is identified as tetrakis(trifiuoromethylthio)ethylene by nuclearmagnetic resonance and elemental analysis.

Analysis.Calcd. for C F S C, 16.8; F, 53.3; S, 30.0. Found: C, 17.4; F,53.9; S, 30.4.

In the dehalogenation process for preparing the com- 9 pounds of theinvention, organicsulfides are employed which have the following generalstructure:

whereinR, W and Ythave the meanings defined previously, i.e., R is anomega-hydroperfluoroalkyl :group, an omegachloroperfluoroalkyl group, ora perfluoroalkyl group; Y is hydrogen, a halogen of atomic :number 9-35(fluorine, chlorine :or bromine) or 'an RS group; :and W is ifluorine oran RS group. X" .is hydrogen, a halogen of atomic number 9-35, or an RSgroup; and Z and Z are halogens of atomic .number 17-53 (chlorine,bromine or iodine). In a preferred form of organic sulfides employed inthe dehalogenation procedure, the carbons of the ethano group arehydrogen-free, i.e., X and Y in theabove formula are halogens of atomicnumber '9-35 or R8 groups.

In the operation of the dehalogenation process, the groups Z and Z inthe above formula are removed by the dehalogenating agent. Powderedmetals, e.g., Zinc, magnesuim, copper and others, are suitable for thispurpose. Zinc is a preferred dehalogenating agent. In this method ofpreparing the compounds, a-corrosion-resistant reaction vessel ischarged with the finely divided .metal. A liquid reaction medium isgenerally added, e.g., an alcohol, ester or ether, in which the metal ismaintained in suspension by agitation. The reaction mixture is heated tothe desired temperature which, conveniently, can be the boiling point ofthe liquid medium. The organic sulfide is added dropwise to the heatedreaction mixture and the combined vapors of the liquid reaction mediumand the reaction products .are passed through a condenser at atemperature which condenses and separates the vapors of the reactionmedium from the volatile reaction products. These products are collectedin a trap cooled by a suitable cooling agent, e.g., a mixture of solidcarbon dioxide and acetone. The products are purified by wellknownconventional methods.

In the dehydrohalogen-ation process for preparing the compounds of theinvention, organic sulfides are employed which have the followinggeneral structure:

The groups R and W have the meanings described previously. X' is ahalogen of atomic number 9-35 or an RS group; Y" is a halogen of atomicnumber 9-35 or an RS group; and Q and Q are hydrogen or halogen ofatomic number 9-53 (fluorine, chlorine, bromine or iodine) with one of Qand Q being hydrogen and the other being halogen.

In the operation of the dehydrohalogenation process, the groups Q and Qin the above formula are removed by the dehydrohalogenating agent.Alkali metal hydroxides are satisfactory dehydrohalogenating agents andthey are preferred for use in the process. For example, the hydroxidesof lithium, sodium or potassium can be employed satisfactorily. In thismethod of preparing the compounds, the alkali metal hydroxide isgenerally charged into a corrosion-resistant reaction vessel and thehydroxide is heated to the temperature at which it melts, generallyabout 130 C. or higher. The hydroxide is maintained in the molten stateand the organic sulfide reactant is passed into the reaction vessel at apoint below the surface of the molten hydroxide. The reaction is rapidand the reaction products, which are volatile, are passed through acondenser into a suitable receiver which is cooled sufficiently tocondense the products. The reaction products are purified byconventional methods, e.g., by fractional distillation through anefficient column, by vapor phase chromatography, by chilling andcrystallizing or by a combination of these and similar well-knownmethods.

The polymers, including homopolymers and copolymers, are soluble in manyorganic liquids, e.g., dimethylformamide, 'butyrolactone, ethylenecarbonate, and the like. Solutions of the polymers obtained from thesulfide monomers are useful as treating agents for porous materials toimpart water repellent properties. For example, a 10% solution of thepolymer of trifluoromethyl trifiuorovinyl sulfide (obtained in ExampleX1) in dimethylformamide is applied to ce'llulosic surfaces (paper,wood) and the treated surfaces are warmed until-all the solvent isremoved. Water applied to the treated surfaces forms droplets which arenot absorbed.

The polyflu-orinated ethylenic sulfides are useful as solvents forhighly fluorinated polymers, e.g., the fiuorinated olefin polymers.Solutions of such polymers, e.g., poly- (tetrafluoroethylene),poly(chlorotrifluoroethylene), and the like in a polyfiuor-oalkylfluorovinyl sulfide are useful in making 'cellulosic compositionsWaterproof. To illusstrate, a 10% by weight solution of a low molecularweight, low-melting'tetrafluoroethylene polymer (melting range 83-150C.) is prepared by warming the polymer in trifiuoromethyl2-chloro-l,2-difiuorovinyl sulfide until the polymer dissolves. Stripsof cellulose filter paper are partly immersed (to about half the lengthof the paper) in the Warm solution for 0.5-1.0 minute. The strips areremoved, and dried in air. The treated area; of the filter paper is notwet by drops of water, whereas the untreated area is immediately andcompletely wetted by water. The treated area of the paper does notsupport combustion, whereas the untreated area burns readily. Equallygood results are obtained by employing approximately 10% solutions oflow-melting tetrafiuoroethylene polymer in 1,2-difluorovinyltrifiuoromethyl sulfide, in 1-bromo-2,2- difluorovinyl trifiuoromethylsulfide, in 1,2 bis(trifluoromethylthio)ethylene intetrakis(trifluoromethylthio)ethylene and in 1,2-bis(trifluoromethylthio -2- (methoxy ethylene as treating agents forcellulose strips and cotton fabr1cs.

As many apparently Widely diiferent embodiments of this invention may bemade without departing from the spirit and scope thereof, it is to beunderstood that this invention is not limited to the specificembodiments thereof except as defined in the appended claims.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. A compound of the formula IFS-(Jinx wherein R has from 1 to 12carbons and is selected from the group consisting ofperfluoroalkyl,w-hydroperfinoroalkyl and w-chloroperfluoroalkyl; W isselected from the group consisting of fluorine and RS; Y is selectedfrom the group consisting of hydrogen, halogen of atomic number of atleast 9 and not more than 35, and RS; and X is selected from the groupconsisting of Y, RS, RD and R' N, wherein R is a hydrocarbon radical ofnot more than 12 carbons and is selected from the group consisting ofalkyl, alkenyl, alkynyl, cyclo-alkyl, aryl, aralkyl, and alkaryl.

2. An ethylenic compound wherein the four valences of the carbons aresatisfied by from 0 to 3 fluorines and from 1 to 4 RS groups, wherein Ris perfluoroalkyl of not more than 8 carbons.

3. An ethylenic compound wherein the four valences of the carbons aresatisfied by from 0 to 3 fluorines and from 1 to 4 RS groups, wherein Ris w-chloroperfluoroalkyl of not more than 8 carbons.

4. An ethylenic compound wherein the four valences of the carbons aresatisfied by from 0 to 3 fluorines and from 1 to 4 RS groups, wherein Ris w-hydroperfluoroalkyl of not more than 8 carbons.

. 1 1 5. A compound of the formula Y F R--S-( J=( JX wherein X and Y arehalogen of the atomic number of at least 9 and not more than 35 and R isperfluoroalkyl of not more than 12 carbons.

6. A compound of the formula f RSC=C-H wherein Y is halogen of at least9 and not more than 35 and R is a perfluoroalkyl group of not more than8 carbons.

7. A compound of the formula i l RSC=CH wherein W is a perfluoroalkylthio group of not more than 8 carbons, and R is a perfluoroalkylgroup of not more than 8 carbons.

8. Polymers having as a recurring unit 9. Polymers according to claim 8,wherein X is hydrogen, Y is halogen of atomic number not less than 9 andnot more than 35, and R is a perfluoroalkyl group of not more than 8carbons.

10. Polymers according to claim 8, wherein X and Y are halogen of atomicnumber not less than 9 and not more than and R is a perfiuoroalkyl groupof not more than 8 carbons.

11. A oopolymer of a polyfluorinated organic sulfide as set forth inclaim 8 with a monomeric ethylenically unsaturated polymerizablecompound selected from the group consisting of styrene, methylmethacrylate, acrylonitrile, divinylbenzene, hexafluoropropene,butadiene, tetrafluoroethylene, and chlorotrifluoroethylene.

14. CF SCH=CHSCF 15. CF SCH=C(SCF )OCH References Cited UNITED STATESPATENTS 2,908,717 10/1959 Johnston 260-609 3,006,964 10/1961 Oestcrling260-608 3,040,086 6/1962 Miller 260 79.7 3,048,569 8/1962 Harris 260-79.7 3,101,377 8/1963 Bluestone 260--609 JOSEPH L. SCHOFER, PrimaryExaminer.

M. LIEBMAN, JAMES A. SEIDLECK, Examiners.

D. K. DENENBERG, D. E. OLSON,

Assistant Examiners.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,326,867 June 20, 1967 John F Harris Jr It is hereby certified thaterror appears in the above numbered patent requiring correction and thatthe said Letters Patent should read as corrected below. a? k Column 1,line 49, strike out "invention which provides a new class ofpolyfluorinated" and insert the same after "present" in line 50, samecolumn 1; column 5, line 51, for "pars" read parts 1-; column 6. line42, for "2 perfluoreethylth-io" resid -2-(perf1uoroethylthio column 10line 59 for "*RS" read R S Signed and sealed this 13th day of August1968.

(SEAL) Attest:

EDWARD J. BRENNER Edward M. Fletcher, Jr.

Commissioner of Patents Attesting Officer

8. POLYMERS HAVING AS A RECURRING UNIT